EP2772967A1 - Composite sous forme de feuille et son procédé de fabrication, et électrode et élément électrochimique utilisant ledit composite - Google Patents

Composite sous forme de feuille et son procédé de fabrication, et électrode et élément électrochimique utilisant ledit composite Download PDF

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Publication number
EP2772967A1
EP2772967A1 EP12844324.9A EP12844324A EP2772967A1 EP 2772967 A1 EP2772967 A1 EP 2772967A1 EP 12844324 A EP12844324 A EP 12844324A EP 2772967 A1 EP2772967 A1 EP 2772967A1
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Prior art keywords
composite
carbon
sheet
binder
composite material
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EP12844324.9A
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German (de)
English (en)
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EP2772967A4 (fr
Inventor
Shunzou Suematsu
Daisuke Horii
Katsuhiko Naoi
Wako Naoi
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Nippon Chemi Con Corp
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Nippon Chemi Con Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a sheet composite of a composite material of an electrode active material and a carbon material molded in a sheet-shape with a fibrous carbon binder, a manufacturing method thereof, and an electrode and an electrochemical element employing this sheet composite.
  • Patent Literatures 1 and 2 An electrode that uses carbon supporting lithium titanate nanoparticles described in Patent Literatures 1 and 2 exerts superior output property, however, there is recently a demand for further improving output property and improving electric conductivity in this type of electrode.
  • an organic binder such as polyvinylidene fluoride (hereinbelow PVDF) was utilized as the binder for preparing the electrode.
  • PVDF polyvinylidene fluoride
  • an organic binder is an insulant, there was a problem that this becomes a factor for reducing output property and energy density. Accordingly, there is an increasing expectation for an electrode that does not utilize an organic binder.
  • the present invention is proposed to solve the problems of the conventional technology described above, the object of which is to provide a sheet composite that can yield an electrode or an electrochemical element which achieves output property and high energy density by molding a composite material of a metal compound capable of occluding and releasing lithium supported on a carbon material into a sheet-form with a fibrous carbon binder, without using an organic binder, as well as a manufacturing method thereof.
  • another object of the present invention is to provide an electrode and an electrochemical element employing the sheet composite.
  • the sheet composite of the present invention comprises a composite material of a metal compound capable of occluding and releasing lithium supported on a carbon material, and the composite material is molded in a sheet-shape with a fibrous carbon binder comprising any of carbon nanotubes, carbon nanofibers, and carbon fibers having a specific surface area of less than 600 m 2 /g.
  • a sheet composite according to the present invention 7 wt% to 200 wt% of the fibrous carbon binder may be added to the composite material.
  • the thickness of the sheet composite may be 20 ⁇ m to 60 ⁇ m.
  • An electrode comprises a collector and the sheet composite formed on a surface of the collector.
  • An electrochemical element employing the electrode is also one aspect of the present invention.
  • the method for manufacturing the sheet composite of the present invention comprises a compositing treatment of supporting a metal compound capable of occluding and releasing lithium on a carbon material to obtain a composite material, a stirring treatment of producing a mixed solution by stirring the composite material with a fibrous carbon binder, and a sheeting treatment of molding the stirred mixed solution in a sheet-shape to obtain a sheet composite, wherein the fibrous carbon binder comprises any of carbon nanotubes, carbon nanofibers, and carbon fibers having a specific surface area of less than 600 m 2 /g.
  • a sheet composite with a non-organic fibrous carbon binder added to a composite material consisting of a metal compound capable of occluding and releasing lithium and a carbon material and molded in a sheet-shape shows high rate property, high output property, and high capacitance property.
  • an electrode and an electrochemical element employing the sheet composite can also realize similar effects.
  • the sheet composite of a metal compound capable of occluding and releasing lithium (hereinbelow, referred to as “metal compound”) and a fibrous carbon binder (hereinbelow, referred to as “fibrous carbon”) according to the present embodiment is:
  • the metal compound, the carbon material, and the fibrous carbon used in the present embodiment will be described below, and manufacturing steps (1) and (2) will be described in detail.
  • the metal compound, the carbon material, and the fibrous carbon used in the present embodiment are those having the following characteristics.
  • oxide metal compounds such as LiCoO 2 , Li 4 Ti 5 O 12 , SnO 2 , and SiO
  • lithium titanate (hereinbelow LTO) can be used as an example of such a metal compound.
  • LTO LTO produced by mixing a titanium source and a lithium source and subjecting to UC treatment can be utilized.
  • a titanium (IV) tetrabutoxy monomer Ti[O(CH 2 ) 3 CH 3 ] 4 , Wako Pure Chemical Industries, Ltd., First Class Grade
  • Ti[O(CH 2 ) 3 CH 3 ] 4 Wako Pure Chemical Industries, Ltd., First Class Grade
  • isopropyl alkoxide and titanium chloride etc. can be utilized.
  • the titanium source solution is prepared by adding acetic acid (CH 3 COOH, Kanto Chemical, Co., Inc., Special Grade) as the chelating reagent and isopropyl alcohol ( (CH 3 ) 2 CHOH, Wako Pure Chemical Industries, Ltd., for Organic Synthesis) as the solvent. Meanwhile, lithium acetate (CH 3 COOLi, Wako Pure Chemical Industries, Ltd., Special Grade) can be employed as the lithium source. Examples of the lithium source other than lithium acetate that can be utilized are lithium hydroxide and lithium carbonate.
  • the Li source solution is prepared by dissolving lithium acetate in a mixed solution of distilled water, acetic acid, and isopropyl alcohol.
  • Examples of the carbon material used in the present embodiment are carbon nanotubes (hereinbelow CNT) or carbon nanofibers (hereinbelow CNF) which have a fibrous structure, Ketjen Black (hereinbelow KB) which is carbon black having a hollow shell structure, carbon black such as acetylene black, amorphous carbon, carbon fiber, natural graphite, artificial graphite, activated carbon, and mesoporous carbon.
  • the carbon material is made into a composite material by mixing with a starting material for the metal compound and subjecting to UC treatment.
  • carbon nanotubes having a fiber diameter of 1 to 10 nm are used.
  • CNF carbon nanofibers
  • CF carbon fibers
  • the fibrous carbon acts as the binder by mixing into the composite material when molding a composite material into a sheet.
  • the fibrous carbon employed in the present embodiment is those having a specific surface area of less than 600 m 2 /g.
  • the composite material used in the treatment of the present embodiment is prepared by adding a starting material for the metal compound to a carbon material and subjecting to UC treatment to allow conjugation.
  • a starting material for the metal compound to a carbon material and subjecting to UC treatment to allow conjugation.
  • the carbon material has a fibrous structure (such as CNT and CNF)
  • ultrahigh pressure dispersion treatment may also be applied with the objective to disperse and homogenize the fibrous structure.
  • the treatment of dispersing the carbon material having fibrous structure by an "ultrahigh pressure dispersion treatment” includes: (a) a mixing treatment; and (b) an ultrahigh pressure dispersion treatment.
  • a carbon material having a fibrous structure and a solvent are mixed to produce a mixed solution.
  • a known method can be employed as the method for mixing the carbon material and the solvent.
  • An example includes mixing by a homogenizer.
  • the ratio of the carbon material and the solvent is preferably 1 L of the solvent to 0.5 to 1 g of the carbon material.
  • a homogenizer is a type of generator that includes: a drive unit; a fixed outer blade; and a rotating inner blade, and performs a line of homogenation via high-speed dispersion - microgrinding - uniformalization. As a result, even dispersion of the composite material and the fibrous carbon binder in the solvent, as well as microgrinding of the fibrous carbon binder are achieved.
  • solvents As the solvent to be mixed with the carbon material having fibrous structure, alcohols, water, and a mixed solvent thereof can be employed.
  • isopropyl alcohol can be used as the solvent.
  • IPA is utilized as the solvent, an advantageous effect of suppressing the aggregation of the carbon material having fibrous structure can take effect.
  • a known method generally referred to as jet mixing jet flow impact mixing
  • a pair of nozzles is set up in a position facing each other on the inner wall of a tubular chamber, and a mixed solution of the carbon material having fibrous structure pressurized by a high-pressure pump is injected from each nozzle and allowed to collide head-on in the chamber.
  • a high-pressure pump is injected from each nozzle and allowed to collide head-on in the chamber.
  • the treatment of the carbon material is performed at a pressure and concentration of 200 MPa, 3 Pass, and 0.5 g/L.
  • the carbon material is added to a solvent such as IPA and mixed to produce a mixed solution.
  • a solvent such as IPA
  • a known method can be employed as the method for mixing this mixed solution.
  • An example includes mixing by a homogenizer.
  • the ratio of the carbon material and the solvent is preferably 1 L of the solvent to 0.5 to 1 g of the carbon material.
  • a metal alkoxide, a lithium compound, and a reaction suppressor are added to a mixed solvent having the carbon material after pretreatment dispersed and subjected to an UC treatment.
  • a metal alkoxide, which is a starting material for the metal oxide active material that is the metal compound, a lithium compound, and a reaction suppressor are added to the carbon material obtained through the ultrahigh pressure dispersion treatment, and subjected to UC treatment which is a mechanochemical reaction.
  • the metal alkoxide, the lithium compound, and the reaction suppressor will be described below.
  • metal alkoxide used in the present embodiment a metal alkoxide capable of occluding and releasing lithium is used.
  • This metal alkoxide is preferably titanium alkoxide, and preferably those where the reaction rate constant of the metal alkoxide hydrolysis reaction is 10 -5 mol -1 sec -1 or higher.
  • Lithium acetate (CH3COOLi, Wako Pure Chemical Industries, Ltd., Special Grade) can be employed as the lithium compound.
  • Examples of the lithium source other than lithium acetate that can be utilized are lithium hydroxide, lithium carbonate, and lithium nitrate.
  • a lithium compound solution can be prepared by dissolving lithium acetate in a mixed solution of distilled water, acetic acid, and isopropyl alcohol.
  • lithium titanate may not be prepared because the reaction was too fast and titanium oxide was formed during preparing lithium titanate.
  • Substances that can form a complex with titanium alkoxide include complexing agents represented by carboxylic acids such as acetic, citric, oxalic, formic, lactic, tartaric, fumaric, succinic, propionic, and levulinic acids, amino polycarboxylic acids such as EDTA, and aminoalcohols such as triethanolamine.
  • carboxylic acids such as acetic, citric, oxalic, formic, lactic, tartaric, fumaric, succinic, propionic, and levulinic acids
  • amino polycarboxylic acids such as EDTA
  • aminoalcohols such as triethanolamine.
  • the UC treatment of the present embodiment can be performed with e.g. a reactor as shown in Figure 9 .
  • the reactor consists of an outer tube 1 having a sheathing board 1-2 at the opening and a rotating inner tube 2 having through-holes 2-1.
  • the reactant inside the inner tube 2 is transferred through the through-holes 2-1 of inner tube 2 to the inner wall 1-3 of the outer tube 1 by its centrifugal force.
  • the reactant collides with the inner wall 1-3 of the outer tube 1 due to the centrifugal force of the inner tube 2, and slides up to the upper portion of the inner wall 1-3 in a thin film state.
  • the thickness of the thin film is 5 mm or less, preferably 2.5 mm or less, and further preferably 1.0 mm or less.
  • the thickness of the thin film can be set by the width of the sheathing board and the amount of the reaction solution.
  • the reaction method of the present embodiment can be realized by the mechanical energy of sheer stress and centrifugal force applied to the reactant, and this sheer stress and centrifugal force are generated by the centrifugal force applied to the reactant inside the inner tube.
  • the centrifugal force applied to the reactant inside the inner tube necessary for the present embodiment is 1500 N (kgms -2 ) or higher, preferably 70000 N (kgms -2 ) or higher, and further preferably 270000 N (kgms -2 ) or higher.
  • the reaction method of the present embodiment above can be applied to various reactions such as a hydrolysis reaction, an oxidation reaction, a polymerization reaction, and a condensation reaction, as long as it is a liquid phase reaction.
  • the above metal compound nanoparticles act as a favorable active material for an electrode for an electrochemical element. In other words, specific surface area will be markedly expanded and output property and capacitance property will be improved by nanosizing.
  • a carbon material supporting highly dispersed metal compound nanoparticles can be obtained.
  • a starting material for the metal compound and a carbon material are introduced into the inner tube of the reactor of Figure 9 , and the inner tube is rotated to mix and disperse the starting material for the metal compound and the carbon material.
  • a catalyst such as sodium hydroxide is further introduced while the inner tube is being rotated so that the hydrolysis and condensation reactions proceed to produce a metal compound, and this metal compound and the carbon material are mixed in a dispersed state.
  • a carbon material supporting highly dispersed metal compound nanoparticle precursor can be formed with the end of the reaction.
  • a highly dispersed metal oxide active material nanoparticle precursor it is desirable to allow a highly dispersed metal oxide active material nanoparticle precursor to be supported on a carbon material by a two-step UC treatment.
  • a first UC treatment a carbon material, a metal alkoxide, and isopropyl alcohol are introduced into the inner tube of the reactor, and the inner tube is rotated to yield a mixed solution of evenly dispersed carbon material and metal alkoxide.
  • a mixed solution comprising a lithium compound, a reaction suppressor, and water is introduced while rotating the inner tube to thereby promote the chemical reaction between the metal alkoxide and the lithium compound, and a carbon material supporting highly dispersed metal compound precursor capable of occluding and releasing lithium is obtained with the end of the reaction.
  • the metal alkoxide and the carbon material are dispersed before starting the chemical reaction with the metal compound capable of occluding and releasing lithium, the metal compound precursor capable of occluding and releasing lithium will be evenly dispersed and supported on the carbon material, and thus aggregation of metal compound nanoparticles will be prevented and output property will be improved.
  • the carbon material supporting a dispersed metal compound precursor capable of occluding and releasing lithium can also be produced by a one-step UC treatment.
  • a carbon material, a metal alkoxide, a reaction suppressor, and water are introduced into the inner tube of the reactor, and the inner tube is rotated to allow mixing and dispersion thereof, while at the same time hydrolysis and condensation reactions are allowed to proceed to promote chemical reaction.
  • a carbon material supporting a dispersed metal compound precursor capable of occluding and releasing lithium can be obtained with the end of the reaction.
  • the product (mixture) obtained through UC treatment is vacuum dried and then calcinated to prepare a composite material of metal compound and carbon material.
  • a mixed solution of the carbon material supporting highly dispersed metal compound precursor obtained by the UC treatment is dried in the range of 85°C to 100°C. This leads to prevention of aggregation of the metal compound as well as improvement of the capacity and output property of electrodes or electrochemical elements that use the electrode material of the present embodiment.
  • the dried carbon material supporting highly dispersed metal compound precursor is subjected to a two-step calcination of e.g. at 300°C for 1 hour and at 900°C for 4 minutes, thereby yielding a composite powder of highly dispersed metal compound nanoparticle supported on carbon material. Further, a short-duration calcination at a high temperature of 900°C yields a metal compound of even composition. As a result, aggregation of the metal compound is prevented, and a composite material of metal compound and carbon material which is crystalline nanoparticles with small particle size can be prepared.
  • the composite material of metal compound and carbon material after the compositing treatment of the composite material and a binder which is a fibrous carbon are added to the solvent and stirred to produce a slurried mixed solution.
  • This mixed solution is molded in a sheet-shape, dried under reduced pressure, and made into a sheet.
  • the pretreatment of dispersing a fibrous carbon binder by ultrahigh pressure dispersion treatment is similar to the pretreatment (a) during the compositing treatment of the composite material described above.
  • a fibrous carbon binder and IPA are mixed to produce a mixed solution, and ultrahigh pressure dispersion treatment is applied to this mixed solution to yield a mixed solution containing dispersed fibrous carbon binder.
  • the composite material after the compositing treatment of the composite material (1) is added and stirred to produce a slurried mixed solution.
  • a homogenizer can be utilized for stirring the mixed solution.
  • a homogenizer is a type of generator, consists of a drive unit, a fixed outer blade, and a rotating inner blade, and performs a line of homogenation via high-speed dispersion - microgrinding - uniformalization. As a result, even dispersion of the composite material and the fibrous carbon binder in the solvent, as well as microgrinding of the fibrous carbon binder are achieved.
  • the mixed solution after the stirring treatment is molded and made into a sheet.
  • the mixed solution is made into a sheet by filtering under reduced pressure with a PTFE filter paper (diameter: 35 mm, average pore size 0.2 ⁇ m) .
  • This sheet is dried under reduced pressure at 60°C for 3 hours.
  • a sheet composite of a composite material and a fibrous carbon can be formed by the treatment above. This sheet composite is subjected to a roller treatment such as pressing if necessary.
  • the sheet composite of the composite material and the fibrous carbon is cut into the same size as a collector of a metal foil such as an aluminum foil, placed on top of the collector, sandwiched with a separately prepared metal foil placed on top thereof, and pressed at a pressure of 10 t/cm 2 for 1 minute from above and under the metal foil to unify the collector with the sheet composite.
  • a sheet composite unified with the collector as such can be made into an electrode of an electrochemical element, i.e. an electrical energy storage electrode, and this electrode shows high output property and high capacitance property.
  • a foil consisting of metal materials such as aluminum, copper, and platinum is employed as the collector, and an etched foil having dents and bumps formed by etching treatment or a plain foil having a flat surface is employed on the surface.
  • the pressing pressure for unifying the collector and the sheet composite is preferably 0.01 to 100 t/cm 2 , and by this pressing, the pressure is applied to the dents and bumps of the surface-expanded etched aluminum foil so that the bumps bite into the molded sheet composite or a portion of the sheet composite is pinched in the dents, and superior conjugation can be rendered.
  • An electrochemical element that can employ this sheet composite and an electrode employing this sheet composite is an electrochemical capacitor or battery that employs an electrolytic solution containing ions of metals such as lithium or magnesium.
  • the electrode of the present embodiment can occlude and desorb metal ions, and works as a negative or positive electrode.
  • an electrochemical capacitor or battery can be configured by laminating the electrode of the present embodiment with an electrode which will be the counter electrode such as an activated carbon, a carbon from which metal ions occlude and desorb, or a metal oxide (with a separator in between), and employing an electrolytic solution containing a metal ion.
  • Example 1 and Comparative Example 1 used in the first property comparison are as follows.
  • LTO is used as the metal compound
  • CNF is used as the carbon material
  • CNT is used as the fibrous carbon added as the binder to this composite material.
  • Example 1 a mixed solution of CNF dispersed in IPA was produced by jet mixing, the mixed solution, titanium alkoxide, and IPA were introduced into the inner tube of the reactor for carrying out an UC treatment, a first UC treatment was performed, a lithium compound, a reaction suppressor, and water were further introduced, and a second UC treatment was performed to yield CNF supporting highly dispersed LTO precursor.
  • This CNF supporting highly dispersed LTO precursor was dried at 90°C, and further calcinated under nitrogen atmosphere at 900°C to yield a composite material of CNF supporting highly dispersed lithium titanate nanoparticles.
  • a mixed solution of a CNT binder dispersed in IPA was produced by jet mixing, the composite material was added to this mixed solution and stirred to prepare a slurried mixed solvent, this was filtered under reduced pressure with a PTFE filter paper (diameter: 35 mm, average pore size 0.2 ⁇ m) , and molded to yield a sheet. This sheet was then dried under reduced pressure at 60°C for 3 hours to form a sheet composite.
  • Comparative Example 1 was similar to Example 1, except that it did not employ a binder upon molding while Example 1 employs a CNT binder upon molding to form a sheet composite.
  • Figure 1 A photograph representing the state of the sheet composite of Example 1 prepared as such is shown in Figure 1 , and a photograph indicating the state of the sheet composite of Comparative Example 1 is shown in Figure 2.
  • Figure 1A is a photograph showing the state of the sheet composite of Example 1
  • Figure 1B is an SEM image of the backside of the sheet composite of Example 1. It is seen from Figure 1A that due to the fibrous CNT acting the binder on the particulate composite material, Example 1 with CNT added as the binder became a self-standing sheet. In addition, it is seen from Figure 1B that composite material particles are not exposed on the surface of the sheet composite because the particulate composite material is evenly placed in the self-standing sheet.
  • Figure 2 is a figure showing the state of the sheet composite of Comparative Example 1. It is seen from Figure 2 that in Comparative Example 1 which did not use a fibrous carbon binder, there was merely an accumulation of a composite material of particulate LTO and CNF. It is seen that since the composite material of LTO and CNF do not have e.g. adherence, attachment, and conjugation effects per se, it is not unified and a sheet is not formed.
  • a fibrous carbon as the binder to a composite material of metal compound and carbon material, a sheet composite as well as an electrode and an electrochemical element employing the sheet composite can be formed, wherein the composite material of the metal compound and the carbon material are evenly placed.
  • Example 2 and Comparative Example 2 used in the second property comparison are as follows.
  • LTO is used as the metal compound
  • CNF is used as the carbon material
  • CNT is used as the fibrous carbon added as the binder to the composite material.
  • Example 2 the sheet composite formed in Example 1 was treated with a roller, this sheet composite was pressed and unified with an etched aluminum foil to prepare an electrode, and an electrochemical cell was prepared by facing this against a lithium foil which will be the counter electrode via a separator employing an electrolytic solution of 1 mole of LiBF 4 as the electrolyte added to 1 L of propylene carbonate (PC) solvent (1M LiBF 4 /PC).
  • PC propylene carbonate
  • Comparative Example 2 a mixed aqueous solution of the composite material described in Example 1 mixed with an organic binder carboxymethylcellulose (CMC) as the binder was prepared, this mixed aqueous solution was applied on an etched aluminum foil, and the solvent (water) was removed to prepare a coated electrode having a coating layer formed on an aluminum foil surface.
  • An electrochemical cell was prepared by facing this coated electrode against a lithium foil which will be the counter electrode via a separator employing an electrolytic solution of 1 mole of LiBF 4 as the electrolyte added to 1 L of propylene carbonate (PC) solvent (1M LiBF 4 /PC).
  • PC propylene carbonate
  • Example 2 will have a higher capacity density compared to Comparative Example 2.
  • an electrode employing a sheet composite with CNT added as the binder to a composite material of a metal compound and CNF will have a larger capacity per unit compared to a coated electrode utilizing an organic binder (CMC) as the binder.
  • CMC organic binder
  • the property comparison was made according to the amount of the fibrous carbon binder added to composite material.
  • Examples 3 to 6 and Comparative Example 3 used in the third property comparison are as follows. In this property comparison, LTO is used as the composite material, CNF is used as the carbon material, and CNT is used as the fibrous carbon added as the binder to the composite material.
  • Example 3 was prepared similarly to the sheet composite of Example 1.
  • the sheet composite was formulated so that the amount of the CNT binder added was 7 wt% of the composite material.
  • Example 4 was prepared similarly to the sheet composite of Example 1.
  • the sheet composite was formulated so that the amount of the CNT binder added was 14 wt% of the composite material.
  • Example 5 was prepared similarly to the sheet composite of Example 1.
  • the sheet composite was formulated so that the amount of the CNT binder added was 20 wt% of the composite material.
  • Example 6 was prepared similarly to the sheet composite of Example 1.
  • the sheet composite was formulated so that the amount of the CNT binder added was 200 wt% of the composite material.
  • Comparative Example 3 similarly to Comparative Example 1, an attempt was made to prepare a sheet electrode that did not employ a binder when molding.
  • the amount of CNT added as the binder is 10 wt% or more of the composite material. Further, a more proper sheet can be prepared by having the amount of CNT at 14 wt% or more. In the meantime, when the sheet composite is made into an electrode, it is desirable that a large amount of LTO is added in order to improve the capacity density. Accordingly, it is desirable that the amount of CNT added as the binder is 50 wt% or less. For a higher capacity density, a sheet having high capacity density can be prepared by having the amount of CNT at 25 wt% or less.
  • a fibrous carbon as the binder to a composite material of LTO as the metal compound and a carbon material, a sheet composite as well as an electrode and an electrochemical element employing the sheet composite having high capacity density wherein the composite material of LTO and the carbon material is evenly placed can be formed.
  • Example 7 a composite material of lithium iron phosphate (hereinbelow LFP) and CNF was used as the composite material of metal compound and carbon material.
  • Example 8 a composite material of LFP and KB was used as the composite material of metal compound and carbon material.
  • An electrochemical cell was prepared by facing this electrode against a lithium foil which will be the counter electrode via a separator employing an electrolytic solution of 1 mole of LiBF 4 as the electrolyte added to 1 L of propylene carbonate (PC) solvent (1M LiBF 4 /PC) as the electrolytic solution.
  • PC propylene carbonate
  • Comparative Example 4 a composite material of LFP and CNF was used as the composite material of metal compound and carbon material.
  • Comparative Example 5 a composite material of LFP and KB was used as the composite material of metal compound and carbon material.
  • PVDF which is an organic binder
  • a coated electrode having a coating layer formed by this mixed solution on an aluminum foil surface was prepared.
  • An electrochemical cell was prepared by facing this electrode against a lithium foil which will be the counter electrode via a separator employing an electrolytic solution of 1 mole of LiBF 4 as the electrolyte added to 1 L of propylene carbonate (PC) solvent (1M LiBF 4 /PC) as the electrolytic solution.
  • PC propylene carbonate
  • Figure 4 is a figure showing the rate property of electrodes using a composite material of LFP and CNF.
  • Figure 5 is a figure showing the rate property of electrodes using a composite material of LFP and KB.
  • Example 7 having a fibrous carbon added as the binder to the composite material shows a higher rate property compared to Comparative Example 4 having an organic binder added as the binder.
  • Example 9 having a fibrous carbon added as the binder to the composite material shows a higher rate property compared to Comparative Example 5 having an organic binder added as the binder.
  • a sheet composite as well as an electrode and an electrochemical element employing the composite having high rate property can also be formed by adding a fibrous carbon as the binder to a composite material employing LFP as the metalized compound and employing CNF or KB as the carbon material.
  • Examples 9 to 11 and Comparative Examples 6 to 8 used in the fifth property comparison are as follows.
  • LTO is used as the metal compound
  • CNF is used as the carbon material
  • CNT is used as the fibrous carbon added as the binder to the composite material.
  • the thickness of the sheet composite formed in Example 2 was set in each of Examples 9 to 11 to prepare electrochemical cells.
  • the thickness of the sheet composite molded in a sheet-shape was 23 ⁇ m.
  • the thickness of the sheet composite molded in a sheet-shape was 50 ⁇ m.
  • the thickness of the sheet composite molded in a sheet-shape was 71 ⁇ m.
  • the thickness of the coating layer of the coated electrode having CMC as the binder was each set similarly to Comparative Example 2 to prepare electrochemical cells.
  • the thickness of the coating layer of the coated electrode was 23 ⁇ m.
  • the thickness of the coating layer of the coated electrode was 50 ⁇ m.
  • the thickness of the coating layer of the coated electrode was 71 ⁇ m.
  • FIG. 6A is a rate property comparison between Example 9 and Comparative Example 6
  • Figure 6B is a rate property comparison between Example 10 and Comparative Example 7
  • Figure 6C is a rate property comparison between Example 11 and Comparative Example 8.
  • a fibrous carbon as the binder to a composite material of LTO as the metal compound and a carbon material, a sheet composite as well as an electrode and an electrochemical element employing the sheet composite having high rate property can be formed regardless of the thickness of the sheet composite.
  • Example 12 and Comparative Example 9 used in the sixth property comparison are as follows.
  • LTO is used as the metal compound
  • CNF is used as the carbon material
  • CNT is used as the fibrous carbon added as the binder to the composite material.
  • Example 12 the thickness of the sheet composites formed in Example 4 were each set.
  • Example 12 and Comparative Example 9 Charge and discharge measurement at an electrode potential of 1.0 to 3.0 V and a C rate of 200 C was performed on cells of Example 12 and Comparative Example 9 prepared as such, and results as shown in Figure 7 were obtained.
  • Figure 7 shows the capacity utilization vs. the thickness of the sheet composite and the coating layer.
  • Figure 7 is a rate property comparison between Example 12 and Comparative Example 9.
  • Example 12 shows a higher evaluation in rate property.
  • the thickness of the sheet composite when the thickness of the sheet composite is less than 20 ⁇ m, the effect of adding CNT as the binder will become less. On the other hand, when the thickness of the sheet composite is greater than 50 ⁇ m, the rate property will be reduced as shown in Figure 7 .
  • a sheet composite as well as an electrode and an electrochemical element employing the sheet composite having high rate property can be formed regardless of the thickness of the sheet composite. Further, in light of the rate property, it is seen that the thickness of the sheet composite is desirably 20 ⁇ m to 50 ⁇ m.
  • the thickness of the sheet composite is 20 ⁇ m to 40 ⁇ m in light of this rate property and the energy density of Figure 6 .
  • an electrochemical element employing a sheet composite having high rate property can be formed regardless of the thickness of the sheet composite. Further, regarding charge and discharge measurement at 100 C, it is seen that high energy density is also retained when the thickness of the sheet composite is 20 ⁇ m to 60 ⁇ m.

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